Highly conductive soluble terpolymers of aniline,toluidine, and o‐aminobenzoic acid/m‐aminobenzenesulfonic acid

Two series of terpolymers, one of o‐/m‐toluidine and aniline with o‐aminobenzoic acid and the other of o‐/m‐toluidine and aniline with m‐aminobenzenesulfonic acid, have been synthesized by oxidative polymerization via an emulsion method with ammonium persulfate as the oxidant and HCl as the external dopant. The terpolymers exhibit excellent solubility and retain the high conductivity (∼1 S cm⁻¹) characteristic of the unsubstituted homopolymer, polyaniline. The terpolymers also possess higher thermal stability than polyaniline. This can be attributed to the presence of internal doping groups and substituents, which introduce flexibility to the otherwise rigid polyaniline backbone. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3040–3048, 2005     

Application of the extended DLVO theory—the stability of alatrofloxacin mesylate solutions

Electrophoretic mobility and contact angle measurements have been made on alatrofloxacin mesylate and its formulations which were protected from or exposed to light, and its degradation product compound (F). In aqueous solution, the light-protected alatrofloxacin mesylate had a zeta-potential of +19 mV, a negligible electron-acceptor (γ_i⁺) surface tension parameter and an electron-donor surface tension parameter γ_i⁻=32.5 mJ m⁻², which was higher than that of water. This caused the particles to be very hydrophilic and to form very stable suspensions in aqueous solution due, mainly, to a net Lewis acid–base (polar) repulsion. After the suspensions were exposed to light, the zeta-potential of the degradation product increassed to +37.8 mV, but the electron-donor surface tension parameter decreased to γ_i⁻=8 mJ m⁻², making the molecules or particles very hydrophobic and causing them to flocculate. The energies of attraction in the latter case were mainly hydrophobic (90%) with about 10% resulting from van der Waals forces.     

Incompressible SPH simulation of water entry of a free‐falling object

In this paper an incompressible smoothed particle hydrodynamics (Incom‐SPH) model is used to simulate the interactions between the free surface flow and a moving object. Incom‐SPH method is a two‐step semi‐implicit hydrodynamic formulation of the SPH algorithm and is capable of accurately treating the free surface deformations and impact forces during the solid–fluid interactions. For a free‐falling object, its motion is tracked by an additional Lagrangian algorithm based on Newton's law to couple with the Incom‐SPH program. The developed model is employed to investigate the water entry of a free‐falling wedge. The accuracy of the computations is validated by the good agreement in predicting the relevant hydrokinematic and hydrodynamic parameters. Finally, a numerical test is performed to study the influence of spatial resolution on the water entry features. The Incom‐SPH modeling coupled with the solid–fluid interaction algorithm could provide a promising computational tool to predict the slamming problems in coastal and offshore engineering. Copyright © 2008 John Wiley & Sons, Ltd.     

Evidence for a new metastable crystalline phase of strontium nitrate

The undercooling of aqueous solutions of strontium nitrate a few mm³ in volume or microsized by dispersion within an emulsion is investigated. The experimental results are consistent with a succession of transformations in undercooled solutions of binaries. Following concentration, the undercoolings are from 14°C to 20°C for macrosamples or from 39°C to 60°C with emulsions. However it is observed that Sr(NO₃)₂ crystallizes into a metastable phase which can be preserved for a long time. The existence of this metastable crystalline phase has been evidenced by Differential Scanning Calorimetry and by an original evaporation method. The phase diagram, including the metastable phase, is presented.     

Reactivity studies of carbon,phosphorus and sulfur‐based acyl sites with tertiary oximes in gemini surfactants

Kinetic studies of the reactions of tertiary oximes (monoisonitroso acetone; MINA and butane 2,3 dione monooxime; BDMO) with some carboxylate (p‐nitrophenyl acetate and p‐nitrophenyl benzoate), phosphate (p‐nitrophenyl diphenyl phosphate and bis (2,4‐dinitrophenyl) phosphate) and sulfonate (p‐nitrophenyl p‐toluene sulphonate) esters in gemini surfactants have been conducted. The observed first‐order rate constant versus surfactant profiles show micelle‐assisted bimolecular reactions involving interfacial ion exchange between bulk aqueous media and micellar pseudophase. Experimental results showed that MINA exhibited better nucleophilic activity towards ester cleavage than BDMO. Pseudophase model has been applied in order to determine micellar second‐order rate constants and binding constants. Copyright © 2013 John Wiley & Sons, Ltd.     

Oxygen‐barrier properties of copolymers based on ethylene terephthalate

The oxygen‐barrier properties of amorphous polyethylene terephthalate‐based copolymers with various acid comonomers were examined. The incorporation of increasing amounts of isophthalate, phthalate, or naphthalate gradually reduced the permeability P toward the low values obtained for the corresponding homopolymers. The permeability of poly(ethylene 3,4′‐bibenzoate) homopolymer was only slightly lower than that of polyethylene terephthalate, and the copolymers correspondingly exhibited a very gradual decrease in P as the amount of 3,4′‐bibenzoate (3,4′BB) increased. In contrast, copolymerization with the linear isomer, 4,4′BB, produced a substantial increase in P. Generally, comonomer affected the solubility S less than the diffusivity D, and therefore changes in P reflected primarily changes in D for the polymers studied. The diffusivity and solubility depended on the copolymer composition in accordance with static and dynamic free‐volume concepts of gas permeability in glassy polymers. The solubility S correlated with the amount of free volume as determined by the glass‐transition temperature. Correlation of the diffusivity D with the magnitude of the subambient γ relaxation identified dynamic free volume with thermally activated conformational changes and segmental motions. Correspondence in the activation energy confirmed the relationship. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1889–1899, 2001     

Influence of (phospho)lipases on properties of mica supported phospholipid layers

The effect of enzymes: lipase from Candida cylindracea (L_Cc), phospholipase A₂ from hog pancreas (PLA₂) and phospholipase C from Bacillus cereus (PLC) to modulate wetting properties of solid supported phospholipid bilayers was studied via advancing and receding contact angle measurements of water, formamide and diiodomethane, and calculation of the surface free energy and its components from van Oss et al. (LWAB) and contact angle hysteresis (CAH) approaches. Simultaneously, topography of the studied layers was determined by Atomic Force Microscopy (AFM). The investigated lipid bilayers were transferred on mica plates from subphase of pure water by means of Langmuir-Blodgett and Langmuir-Schaefer techniques. The investigated phospolipid layers were: saturated DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine), unsaturated DOPC (1,2-dioleoyl-sn-glycero-3-phosphocholine), and their mixture DPPC/DOPC. The obtained results revealed that the lipid membrane degradation by the enzymes caused increase in its surface free energy due to the amphiphilic hydrolysis products, which may accumulate in the lipid bilayer. In result activity of the enzymes may increase and then break down the bilayer structure takes place. It is likely that after dissolution of the hydrolysis reaction products in the bulk phase, patches of bare mica surface are accessible, which contribute to the apparent surface free energy changes. Comparison of AFM images and the free energy changes of the layers gives better insight into changes of their properties. The observed gradual increase in the layer surface free energy allows controlling of the hydrolysis process to obtain the surfaces of defined properties.